CN109326587A - A kind of three-in-one compound photodetector and preparation method thereof from driving - Google Patents
A kind of three-in-one compound photodetector and preparation method thereof from driving Download PDFInfo
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- CN109326587A CN109326587A CN201811181613.4A CN201811181613A CN109326587A CN 109326587 A CN109326587 A CN 109326587A CN 201811181613 A CN201811181613 A CN 201811181613A CN 109326587 A CN109326587 A CN 109326587A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/16—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits
- H01L25/167—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits comprising optoelectronic devices, e.g. LED, photodiodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/16—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits
- H01L25/162—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits the devices being mounted on two or more different substrates
Abstract
The invention discloses a kind of three-in-one compound photodetectors and preparation method thereof from driving, it is driven using perovskite solar battery, thermoelectric generation film, the parallel connection of pressure electricity-generating piece as the voltage of perovskite photodetector, perovskite solar battery, thermoelectric generation film, pressure electricity-generating piece can be individually for perovskite photodetector and provide voltage, thermoelectric generation film converts heat into electric energy simultaneously, external kinetic energy is converted to electric energy by pressure electricity-generating piece, promotes the influence of the performance and used life of device.The photodetector stability that photoelectric heat prepared by the present invention replies conjunction from driving by cable is good, and long service life realizes round-the-clock optical detection.
Description
Technical field
The invention belongs to technical field of electronic devices, further relate to the conjunction of one of semiconductor light electro-technical field three
The one compound photodetector and preparation method thereof from driving.Photodetector of the invention can be used for detecting ultraviolet-visible light-
The optical signal of near infrared band.
Background technique
Photodetector be it is a kind of optical radiation energy is converted into a kind of physical quantity photoelectric device convenient for measurement, in military affairs
It has a wide range of applications with the every field of national economy, such as bio-sensing, optical imagery, optic communication, environmental monitoring, national defence
Military project etc..The principle of photodetector mainly utilizes external photoeffect or inner photoeffect, and the electronics in detector is directly inhaled
The energy for receiving photon, makes motion state change and generates electric signal, is usually used in detecting infra-red radiation and visible light.It is close several
Year, with the development of science and technology, having there is the photodetector of more and more types to occur.
Paper " the High-Performance Flexible Broadband that the authors such as Xin Hu deliver at it
Photodetector Based on Organolead Halide Perovskite”(Advanced Functional
Materials, vol.24, pp.7373-7380,2014) in disclose a kind of organohalogen compounds perovskite photodetector.It should
Although organohalogen compounds perovskite photodetector is on the basis of traditional perovskite photodetector advantage, using spin coating method system
For MAPbI3Film, foring structure is ITO/MAPbI3The coplanar device of/ITO, can be real by carrying out external power supply to device
Existing wide range photodetection, still, the shortcoming which still has is the perovskite photodetector
It needs applied voltage to drive at work, leads to not the application in the case where needing prolonged optical detection occasion.
The patented technology that University Of Suzhou possesses at it is " in conjunction with the driving photodetection certainly of solar battery and photodetector
One kind is disclosed in system and preparation method thereof " (application number: 201510969469.0 Authorization Notice No.: CN105575964 B)
In conjunction with the device architecture and preparation method of solar battery and photodetector.The method that the structure of the patented technology uses spin coating
It prepares perovskite solar battery to drive as voltage, perovskite detector is optoelectronic sensor.The device architecture exist with
Lower two o'clock shortcoming is, first, leading to perovskite too since conversion ratio of the perovskite solar battery for solar energy be not high
During the voltage driving as photodetector, solar energy is dissipated in the form of thermal energy positive energy battery mostly, simultaneously
The thermal energy of dissipation has a great impact to stability and the service life aspect of the performance especially device of entire device.Second,
Photoelectric conversion can not be carried out at night and perovskite solar battery rainy days, the photodetector is caused to can not work normally.
Perovskite solar battery and perovskite photodetector are mainly connected in the preparation method of the patented technology using fine copper wire,
Thus leading to its existing shortcoming is that perovskite solar battery and perovskite photodetector are connected using fine copper wire
It is at high cost, stability is poor.
Summary of the invention
It is an object of the invention in view of the deficiency of the prior art, provide the three-in-one compound driving certainly of one kind
Photodetector realizes that photodetector does not need that optical detection can be carried out for a long time by extra power.
The concrete thought for realizing the object of the invention is to utilize perovskite solar battery, thermoelectric generation film and pressure electricity-generating
Plate parallel connection drives as the external voltage of photodetector, realizes for a long time from the optical detection of driving.Perovskite solar battery,
The parallel connection of thermoelectric generation film, pressure electricity-generating plate can not only reduce generating in perovskite solar cell photoelectric conversion process
Influence of the thermal energy to device performance, and these thermal energy can be converted to electric energy, meanwhile, at night and rainy weather, utilize
The thermo-electric generation and pressure electricity-generating plate of thermoelectric generation film the external energies such as the kinetic energy of raindrop are converted into electric energy provide voltage into
Row optical detection.
The three-in-one compound photodetector from driving of the invention, including perovskite solar battery, glass substrate,
Hole transmission layer, light absorbing layer, the electron transfer layer being from top to bottom sequentially prepared on the substrate of the perovskite solar battery
And metal electrode；Light absorbing layer is prepared in the glass substrate, prepares two metal electrodes in the two sides of light absorbing layer；It is described
Photodetector further includes thermoelectric generation film, pressure electricity-generating plate, and the gold of perovskite solar cell is arranged in the thermoelectric generation film
Belong to the lower surface of electrode；The lower surface of thermoelectric generation film, the perovskite solar battery, temperature is arranged in the pressure electricity-generating plate
It connects again with perovskite photodetector after poor power generation sheet, pressure electricity-generating plate three are in parallel.
The three-in-one compound photodetector preparation method from driving of the invention, connects calcium titanium using inkjet printing technology
Mine solar battery, thermoelectric generation film, pressure electricity-generating plate, perovskite photodetector；The step of this method includes the following:
(1) perovskite solar cell substrate is pre-processed:
Substrate is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, surpassed in deionized water by (1a)
Sound cleaning；
The substrate being cleaned by ultrasonic is carried out UV ozone UV-zone processing by (1b), obtains the substrate pre-processed；
(2) hole transmission layer of perovskite solar battery is prepared:
By hole transmission layer precursor solution drop on the substrate pre-processed, spin coating is carried out using sol evenning machine, after spin coating
Substrate be placed in thermal station and anneal, obtain the hole transmission layer of perovskite solar battery；
(3) solution coating method is used, the light absorbing layer of perovskite solar battery is prepared；
(4) electron transfer layer of perovskite solar battery is prepared:
Electron transfer layer precursor solution is spin-coated on the light absorbing layer that preparation is completed using sol evenning machine, obtains perovskite too
The electron transfer layer of positive energy battery；
(5) vacuum coater is used, the metal electrode of perovskite solar battery is prepared；
(6) heat-conducting silicone grease is used, the cell metallic electrode and thermoelectric generation film to perovskite solar energy carry out physical connection；
(7) positive electrode of pressure electricity-generating plate is adhered to the lower surface of the huyashi-chuuka (cold chinese-style noodles) layer of thermoelectric generation film；
(8) glass substrate of perovskite photodetector is pre-processed:
The glass substrate of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound clearly
It washes, is dried up using high-purity nitrogen；
(9) solution coating method is used, the light absorbing layer of perovskite photodetector is prepared；
(10) vacuum coater is used, two metal electrodes of perovskite photodetector are prepared；
(11) perovskite solar battery, thermoelectric generation film, perovskite photodetector are connected:
Using inkjet printing technology, by the substrate of perovskite solar battery respectively with the anode of thermoelectric generation film, pressure
The metal electrode connection of the positive electrode, perovskite photodetector of power generation plate, by the metal electricity of perovskite solar battery
Pole respectively with the cathode of thermoelectric generation film, the negative electrode of pressure electricity-generating plate, perovskite photodetector another metal electrode
Connection.
Compared with prior art, the present invention has the advantage that
First, after using perovskite solar battery, thermoelectric generation film and the three's parallel connection of pressure electricity-generating plate due to the present invention
It connects again with perovskite photodetector, overcomes photodetector and applied voltage is needed to drive at work, lead to not
The shortcomings that needing the application under prolonged optical detection occasion, so that the three-in-one compound photodetection from driving of the invention
Device does not need that optical detection can be carried out for a long time by extra power.
Second, since the present invention is in parallel using perovskite solar battery, thermoelectric generation film and pressure electricity-generating plate three, make
The power supply of perovskite photodetector can be individually for by obtaining perovskite solar battery, thermoelectric generation film and pressure electricity-generating plate three, and
And the thermal energy generated in perovskite solar cell photoelectric conversion process can be converted to electric energy, pressure electricity-generating by thermoelectric generation film
The external energies such as kinetic energy of raindrop, wind-force can be converted to electric energy by plate, following two disadvantage be overcome, first, due to perovskite
Solar battery is not high for the conversion ratio of solar energy, causes perovskite solar battery in the voltage drive as photodetector
During dynamic, solar energy is dissipated in the form of thermal energy mostly, at the same the thermal energy to dissipate to the performance of entire device especially
Have a great impact in terms of the stability and service life of device；Second, since perovskite solar battery is at night and wet weather
Weather can not carry out photoelectric conversion, and the photodetector is caused to can not work normally.So that three-in-one compound self-powered of the invention
The stability and service life of dynamic photodetector get a promotion, and can realize round-the-clock optical detection.
Third, due to using inkjet printing technology to connect perovskite solar battery, the temperature difference in preparation process of the invention
Power generation sheet, perovskite photodetector overcome the prior art and the problem that metal connecting line is at high cost, stability is poor are used to adopt
At low cost with preparation process of the invention, stock utilization is high, and preparation efficiency is high, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of photodetector of the present invention；
Fig. 2 is the process flow chart of photodetector preparation method of the present invention.
Specific embodiment
The present invention is described further with reference to the accompanying drawings and examples.
Referring to Fig.1, the structure of the three-in-one compound photodetector from driving of the invention is further described.
The three-in-one compound photodetector from driving of the present invention, including perovskite solar battery, glass substrate 8,
Hole transmission layer 2, the light absorbing layer being from top to bottom sequentially prepared on the substrate 1 of the perovskite solar battery), electron-transport
Layer 4 and metal electrode 5.Light absorbing layer 9 is prepared in the glass substrate 8, prepares two metal electricity in the two sides of light absorbing layer 9
Pole 10 and 11.The photodetector further includes thermoelectric generation film 6, pressure electricity-generating plate 7, and the thermoelectric generation film 6 is arranged in calcium
The lower surface of the metal electrode 5 of titanium ore solar cell.The lower surface of thermoelectric generation film 6 is arranged in the pressure electricity-generating plate 7, described
It connects again with perovskite photodetector after perovskite solar battery, thermoelectric generation film, pressure electricity-generating plate three are in parallel.
The solar cell substrate 1 uses tin indium oxide ITO or fluorine-doped tin oxide FTO substrate.
Inkjet printing is utilized to a kind of three-in-one compound photodetector preparation method from driving of the invention referring to Fig. 2
Technology connects perovskite solar battery, thermoelectric generation film, pressure electricity-generating plate, perovskite photodetector；The step of this method
Including as follows.
Step 1, perovskite solar cell substrate is pre-processed.
Substrate 1 is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, that ultrasound is carried out in deionized water is clear
It washes.
The substrate 1 being cleaned by ultrasonic is subjected to UV ozone UV-zone processing, obtains the substrate 1 pre-processed.
Step 2, the hole transmission layer of perovskite solar battery is prepared.
By hole transmission layer precursor solution drop on the substrate 1 pre-processed, spin coating is carried out using sol evenning machine, after spin coating
Substrate 1 be placed in thermal station and anneal, obtain the hole transmission layer 2 of perovskite solar battery.
The hole transmission layer precursor solution refers to, triphenylamine derivative solution, poly- 3,4-ethylene dioxythiophene: polyphenyl
Vinyl sulfonate PEDOT:PSS solution, poly- (3- hexyl thiophene) P3HT solution, cuprous sulfocyanide CuSCN solution, nickel oxide NiO
Any one in solution.
Step 3, using solution coating method, the light absorbing layer 3 of perovskite solar battery is prepared.
The solution coating method refers to, using any one in three kinds of one-step method spin coating, two-step method spin coating, blade coating methods
Kind method.
The light absorbing layer refers to that structure is ABX3Any one in the perovskite material of type, wherein A is MA+、FA+、
(CsxMA1-x)+、(CsxFA1-x)+、(FAxMA1-x)+、(CsxFAyMA1-x-y)+One of, B Pb2+, X I-And
(IxBr1-x)-、(ClxI1-x)-、(ClxBr1-x)-、(I1-x-yBrxCly)-One of.
Step 4, the electron transfer layer of perovskite solar battery is prepared.
Electron transfer layer precursor solution is spin-coated on the light absorbing layer 3 that preparation is completed using sol evenning machine, obtains perovskite
The electron transfer layer 4 of solar battery.
The electron transfer layer precursor solution refers to, zinc oxide ZnO solution, stannic oxide SnO2Solution, C60Solution,
[6,6] any one in-phenyl C61 methyl butyrate PCBM solution.
Step 5, using vacuum coater, the metal electrode 5 of perovskite solar battery is prepared.
The metal electrode is using any one in gold Au, silver Ag, with a thickness of 100~300nm.
Step 6, using heat-conducting silicone grease, cell metallic electrode 5 and thermoelectric generation film 6 to perovskite solar energy carry out physics
Connection.
Step 7, the positive electrode of pressure electricity-generating plate 7 is adhered to the lower surface of the huyashi-chuuka (cold chinese-style noodles) layer of thermoelectric generation film 6.
Step 8, the glass substrate of perovskite photodetector is pre-processed.
The glass substrate 8 of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound
Cleaning, is dried up using high-purity nitrogen.
Step 9, using solution coating method, the light absorbing layer 9 of perovskite photodetector is prepared.
The solution coating method refers to, using any one in three kinds of one-step method spin coating, two-step method spin coating, blade coating methods
Kind method.
The light absorbing layer refers to that structure is ABX3Any one in the perovskite material of type, wherein A is MA+、FA+、
(CsxMA1-x)+、(CsxFA1-x)+、(FAxMA1-x)+、(CsxFAyMA1-x-y)+One of, B Pb2+, X I-And
(IxBr1-x)-、(ClxI1-x)-、(ClxBr1-x)-、(I1-x-yBrxCly)-One of.
Step 10, using vacuum coater, two metal electrodes 10 and 11 of perovskite photodetector are prepared.
The metal electrode is using any one in gold Au, silver Ag, with a thickness of 100~300nm.
Step 11, perovskite solar battery, thermoelectric generation film, perovskite photodetector are connected.
Using inkjet printing technology, by the substrate 1 of perovskite solar battery respectively with the anode of thermoelectric generation film 6, pressure
A metal electrode 10 connection of the positive electrode, perovskite photodetector of power power generation plate 7, by the gold of perovskite solar battery
Belong to electrode 5 respectively with the cathode of thermoelectric generation film 6, the negative electrode of pressure electricity-generating plate 7, perovskite photodetector another gold
Belong to electrode 11 to connect.
The sintering temperature of the inkjet printing technology is 80~120 DEG C, and the time is 10~15min.
The thermal energy generated in perovskite solar cell photoelectric conversion process is transmitted to thermoelectric generation film hot-face layer, temperature difference hair
Semiconductor layer among electric piece utilizes the thermo-electric generation of hot-face layer and huyashi-chuuka (cold chinese-style noodles) layer, converts heat energy into electric energy, reduces thermal energy to calcium
The influence of titanium ore photodetector promotes the performance and service life of device.Permanent magnet among pressure electricity-generating plate electrode passes through
Homopolarity is attracting, and the heteropolar principle repelled each other is in suspension, and by the extruding of the external environments such as the strike of raindrop, permanent magnet has coil to cut
It cuts magnetic induction line to produce electricl energy, power for perovskite photodetector.
Using inkjet printing technology by perovskite solar battery, thermoelectric generation film and pressure electricity-generating plate three it is in parallel after again
It connects with perovskite photodetector, allows perovskite solar battery, thermoelectric generation film and the pressure electricity-generating plate three to be
Perovskite photodetector is individually powered, and daytime is mainly that perovskite solar battery is powered for perovskite detector, at night
And rainy weather, the external energies such as the kinetic energy of raindrop are converted into electricity using the thermo-electric generation and pressure electricity-generating plate of thermoelectric generation film
It can be that perovskite photodetector is powered.
Preparation process of the invention is described further below with reference to three embodiments.
Embodiment 1:
Step 1 pre-processes perovskite solar cell substrate.
Tin indium oxide ITO substrate 1 is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, deionized water
In be cleaned by ultrasonic, the cleaning temperature of ultrasonic cleaning is 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min.
The tin indium oxide ITO substrate 1 being cleaned by ultrasonic is subjected to UV-zone and handles 30min, obtains the oxidation pre-processed
Indium tin ITO substrate 1.
Step 2 prepares the hole transmission layer of perovskite solar battery.
The 35mg CuSCN salt of 99% concentration is dissolved in the 1mL diethyl thioether of 98% concentration, at room temperature constant temperature
CuSCN solution is prepared in 30 minutes in stirring, and the CuSCN solution of 35 μ L is spin-coated on to the tin indium oxide ITO substrate 1 pre-processed
On, revolving speed 5000rpm, spin coating 30s obtain the hole transmission layer 2 of perovskite solar battery.
Step 3 prepares the light absorbing layer of perovskite solar battery.
Perovskite precursor solution is prepared, according to dimethyl sulfoxide: the volume of gamma-hydroxybutyric acid lactone DMSO:GBL=3:7
Than preparing mixed solvent, jog is allowed to be sufficiently mixed after mixing, and the methylpyridinium iodide ammonium MAI of 215mg is taken to be dissolved in above-mentioned 1mL mixing
In solvent, methylpyridinium iodide ammonium MAI solution is obtained, the lead iodide PbI of 640mg is taken2, methylpyridinium iodide ammonium with the 1mL of above-mentioned preparation
The mixing of MAI solution, 75 DEG C of heating stirrings obtain MAPbI up to being completely dissolved3Solution.
Configured solution is placed on 60 DEG C of heating in thermal station, it is rear to accelerate with the revolving speed spin coating 20s of 1000rpm
4000rpm spin coating 30s again is added dropwise toluene in total time 45s, is placed in thermal station later, and annealing temperature is 100 DEG C, when annealing
Between be 20min, obtain the light absorbing layer 3 of perovskite solar cell.
Step 4 prepares the electron transfer layer of perovskite solar battery.
By [6,6]-phenyl C of 20mg in glove box61Methyl butyrate PCBM is dissolved in the chlorobenzene of 1mL, is stirred with magnetic force
Mixing platform and stirring 8 hours dissolves it sufficiently, and being with revolving speed using sol evenning machine is that 45s carries out spin coating the 2000rpm time, obtains electronics
Transport layer 4.
Step 4 prepares the metal electrode of perovskite solar battery.
It is 10 in Chamber vacuum degree condition-5Pa hereinafter, withRate vapor deposition 100nm Ag, obtain metal electrode
5, perovskite solar battery is completed in preparation.
Step 6, using heat-conducting silicone grease, cell metallic electrode 5 and thermoelectric generation film 6 to perovskite solar energy carry out physics
Connection.
The positive electrode of pressure electricity-generating plate 7 is adhered to the following table of the huyashi-chuuka (cold chinese-style noodles) layer of thermoelectric generation film 6 using adhesive by step 7
Face.
Step 8 pre-processes the glass substrate of perovskite photodetector.
The glass substrate 8 of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound
Cleaning, cleaning temperature are 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min, is then dried up using high-purity nitrogen.
Step 9 prepares the light absorbing layer of perovskite photodetector.
By the iodine methylamine CH of 99% concentration3NH3The lead iodide PbI of I and 99% concentration21:1 is dissolved in 1mLN-N bis- in molar ratio
In methylformamide DMF, perovskite precursor solution is formed, and heating stirring 8h dissolves it sufficiently at 60 DEG C, with 2000rpm
Revolving speed spin coating 20s, it is rear to accelerate 5000rpm spin coating 30s again, toluene is added dropwise in total time 45s, being placed in temperature later is 100
Anneal 15min in DEG C thermal station, obtains the light absorbing layer 9 of perovskite photodetector.
Step 10 prepares two metal electrodes of perovskite photodetector.
The glass substrate that the light absorbing layer of perovskite photodetector is completed in above-mentioned preparation is put into vacuum chamber, by covering
Film version is deposited to obtain the electrode 11 of the Au electrode 10 of 300nm.
Step 11 connects perovskite solar battery, thermoelectric generation film, perovskite photodetector.
Using inkjet printing technology, sintering temperature is 100 DEG C, time 10min, by the substrate of perovskite solar battery
1 respectively with the anode of thermoelectric generation film 6, the positive electrode of pressure electricity-generating plate 7, perovskite photodetector a metal electrode 10
Connection, by the metal electrode 5 of the perovskite solar battery negative electricity with the cathode of thermoelectric generation film 6, pressure electricity-generating plate 7 respectively
Another metal electrode 11 connection of pole, perovskite photodetector.
Embodiment 2:
Step 1: pretreatment perovskite solar cell substrate.
By fluorine-doped tin oxide FTO substrate 1 be sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, go from
It is cleaned by ultrasonic in sub- water, the cleaning temperature of ultrasonic cleaning is 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min.
The fluorine-doped tin oxide FTO substrate 1 being cleaned by ultrasonic is subjected to UV-zone and handles 30min, obtains having pre-processed
Fluorine-doped tin oxide FTO substrate 1.
Step 2: the hole transmission layer of perovskite solar battery is prepared.
Under magnetic stirring by the NiCl of 12.885g2·6H2O is dissolved in the deionized water of 100mL, is added dropwise
For 10MNaOH solution until pH value reaches 10, precipitating is washed with deionized twice in the muddy green solution centrifugation that will be obtained,
It is later that powder is dry at 80 DEG C, 2 hours are then annealed at different temperatures by 150mg NiOxNano particle is added to 5mL
In isopropanol, then the mixing liquid is ultrasonically treated in ultrasonic cleaner with the power of 100W, ultrasonication it is total
Time is about 8 hours.Acquired solution is filtered by the polytetrafluoroethylene (PTFE) TPFE filter of 0.45um.
Using spin-coating method, by obtained solution with the revolving speed of 2000rpm in the fluorine-doped tin oxide FTO substrate pre-processed
Spin coating 30s on 1, then anneal at 120 DEG C 20min, obtains the hole transmission layer 2 of perovskite solar battery.
Step 3: the light absorbing layer of perovskite solar battery is prepared.
Perovskite precursor solution is prepared, according to dimethyl sulfoxide: the volume of gamma-hydroxybutyric acid lactone DMSO:GBL=3:7
Than preparing mixed solvent, jog is allowed to be sufficiently mixed after mixing, and the methylpyridinium iodide ammonium MAI of 215mg is taken to be dissolved in above-mentioned 1mL mixing
In solvent, methylpyridinium iodide ammonium MAI solution is obtained, the lead iodide PbI of 640mg is taken2, methylpyridinium iodide ammonium with the 1mL of above-mentioned preparation
The mixing of MAI solution, 75 DEG C of heating stirrings obtain MAPbI up to being completely dissolved3Solution.
In humidity 5%, the atmospheric environment that 25 DEG C of temperature, adjustment blade coating platform to assigned temperature adjusts scraper height extremely
1230 microns, fluorine-doped tin oxide FTO substrate 1 is placed on blade coating platform preheats 1 minute later, take perovskite precursor solution
20 microlitres are added dropwise in substrate, drive scraper at the uniform velocity to advance blade coating according to the speed of setting later, will be coated with perovskite has active layer
Substrate is placed in thermal station, and annealing temperature is 100 DEG C, and anneal 30min, obtains perovskite light absorbing layer 3.
Step 4: the electron transfer layer of perovskite solar battery is prepared.
2.95g acetic acid zinc powder is added in 125mL methanol solution, is warming up to 70 DEG C immediately, is stirred continuously to obtain
Prescribed liquid A；In the methanol solution that 1.48g potassium hydroxide powder is dissolved in 65mL at 70 DEG C, it is stirred continuously to obtain mixed solution
B；Solution B is added dropwise to solution A dropwise in stirring, then stirs 2h, after standing allows to cool to room temperature, removal upper layer is clear
70mL n-butanol, 5mL methanol and 5mL chloroform are added in precipitating, at the uniform velocity stir after cleaning precipitating with methanol by liquid, filter
Obtain zinc oxide nano-particle solution.
By burnett's solution with the revolving speed spin coating 30s on the perovskite light absorbing layer 3 that preparation is completed, repetition for 3000rmp
Spin coating three times, obtains electron transfer layer 4.
Step 5: the metal electrode of perovskite solar battery is prepared.
It is 10 in Chamber vacuum degree condition-5Pa hereinafter, withRate vapor deposition 100nm Ag, obtain metal electrode
5, perovskite solar battery is completed in preparation.
Step 6: using heat-conducting silicone grease, and the cell metallic electrode 5 and thermoelectric generation film 6 to perovskite solar energy carry out object
Reason connection.
Step 7: adhesive is used, the positive electrode of pressure electricity-generating plate 7 is adhered under the huyashi-chuuka (cold chinese-style noodles) layer of thermoelectric generation film 6
Surface.
Step 8: the glass substrate of pretreatment perovskite photodetector.
The glass substrate 8 of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound
Cleaning, cleaning temperature are 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min, is then dried up using high-purity nitrogen.
Step 9: the light absorbing layer of perovskite photodetector is prepared.
By the iodine methylamine CH of 99% concentration3NH3The lead iodide PbI of I and 99% concentration21:1 is dissolved in 1mLN-N bis- in molar ratio
In methylformamide DMF, perovskite precursor solution is formed, and heating stirring 8h dissolves it sufficiently at 60 DEG C, is in humidity
Under the conditions of 120 DEG C of 40%, perovskite precursor solution is dropped in above-mentioned substrate of glass, control scraper is at a distance from substrate
100um, and it is at the uniform velocity passed through into substrate, it is uniformly coated on perovskite solution on glass basic surface, perovskite will be coated with
There is the substrate of active layer to be placed in thermal station, annealing temperature is 100 DEG C, and anneal 15min, and the light for obtaining perovskite photodetector is inhaled
Receive layer 9.
Step 10: two metal electrodes of perovskite photodetector are prepared.
The glass substrate that the light absorbing layer of perovskite photodetector is completed in above-mentioned preparation is put into vacuum chamber, by covering
Film version is deposited to obtain the electrode 11 of the Au electrode 10 of 300nm.
Step 11: connection perovskite solar battery, thermoelectric generation film, perovskite photodetector.
Using inkjet printing technology, sintering temperature is 100 DEG C, time 10min, by the substrate of perovskite solar battery
1 respectively with the anode of thermoelectric generation film 6, the positive electrode of pressure electricity-generating plate 7, perovskite photodetector a metal electrode 10
Connection, by the metal electrode 5 of the perovskite solar battery negative electricity with the cathode of thermoelectric generation film 6, pressure electricity-generating plate 7 respectively
Another metal electrode 11 connection of pole, perovskite photodetector.
Embodiment 3:
Step A pre-processes perovskite solar cell substrate.
Tin indium oxide ITO substrate 1 is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, deionized water
In be cleaned by ultrasonic, the cleaning temperature of ultrasonic cleaning is 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min.
The tin indium oxide ITO substrate 1 being cleaned by ultrasonic is subjected to UV-zone and handles 30min, obtains the oxidation pre-processed
Indium tin ITO substrate 1.
Step B prepares the hole transmission layer of perovskite solar battery.
Take filtered 3,4-ethylene dioxythiophene: poly styrene sulfonate PEDOT:PSS (P VP Al 4083) drop exists
On the tin indium oxide ITO substrate 1 pre-processed, using sol evenning machine carry out spin coating, spin coating revolving speed be 6000rmp, time 48s,
Then 150 DEG C of annealing 15min in thermal station, obtain the hole transmission layer 2 of perovskite solar battery.
Step C prepares the light absorbing layer of perovskite solar battery.
1.36M PbI2 and 0.24M PbCl2 are dissolved in DMF, 75 DEG C is heated and stirs 2 hours.The MAI's and 30mg of 70mg
FAI is dissolved in the IPA of 1mL, additionally incorporates the DMF of 10 μ L.Later, PbX2Precursor solution spin coating on substrate, revolving speed 3000rpm
Spin-coating time 45s, the mixed solution of MAI and FAI is spin-coated on PbX later2On substrate, revolving speed 3000rpm spin-coating time 45s.It
Sample obtains the light absorbing layer 3 of perovskite solar cell in 100 DEG C of thermal station annealing 10min afterwards.
Step D prepares the electron transfer layer of perovskite solar battery.
By [6,6]-phenyl C of 20mg in glove box61Methyl butyrate PCBM is dissolved in the chlorobenzene of 1mL, is stirred with magnetic force
Mixing platform and stirring 8 hours dissolves it sufficiently, and being with revolving speed using sol evenning machine is that 45s carries out spin coating the 2000rpm time, obtains electronics
Transport layer 4.
Step E prepares the metal electrode of perovskite solar battery.
It is 10 in Chamber vacuum degree condition-5Pa hereinafter, withRate vapor deposition 100nm Ag, obtain metal electrode
5, perovskite solar battery is completed in preparation.
Step F, using heat-conducting silicone grease, cell metallic electrode 5 and thermoelectric generation film 6 to perovskite solar energy carry out physics
Connection.
The positive electrode of pressure electricity-generating plate 7 is adhered to the following table of the huyashi-chuuka (cold chinese-style noodles) layer of thermoelectric generation film 6 using adhesive by step G
Face.
Step H pre-processes the glass substrate of perovskite photodetector.
The glass substrate 8 of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound
Cleaning, cleaning temperature are 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min, is then dried up using high-purity nitrogen.
Step I prepares the light absorbing layer of perovskite photodetector.
0.46M PbI2 is dissolved in DMF, is that 2000rpm is spun on hole transport layer surface, time 40s with revolving speed；Rotation
It is painted with to be placed in glove box and stands 10 minutes or anneal at a temperature of 70 DEG C 2 minutes to remove remaining DMF solvent；Immediately
, the MAI that concentration is 50mg/mL is spun on PbI2 layer, revolving speed 4000rpm, time 35s；Sample is placed in heat later
Platform is annealed, and annealing temperature is 100 DEG C, annealing time 20min, obtains the light absorbing layer 9 of perovskite photodetector.
Step J prepares two metal electrodes of perovskite photodetector.
The glass substrate that the light absorbing layer of perovskite photodetector is completed in above-mentioned preparation is put into vacuum chamber, by covering
Film version is deposited to obtain the electrode 11 of the Au electrode 10 of 300nm.
Step K connects perovskite solar battery, thermoelectric generation film, perovskite photodetector.
Using inkjet printing technology, sintering temperature is 100 DEG C, time 10min, by the substrate of perovskite solar battery
1 respectively with the anode of thermoelectric generation film 6, the positive electrode of pressure electricity-generating plate 7, perovskite photodetector a metal electrode 10
Connection, by the metal electrode 5 of the perovskite solar battery negative electricity with the cathode of thermoelectric generation film 6, pressure electricity-generating plate 7 respectively
Another metal electrode 11 connection of pole, perovskite photodetector.
Claims (9)
1. a kind of three-in-one compound photodetector from driving, including perovskite solar battery, glass substrate (8), in institute
State the hole transmission layer (2) being from top to bottom sequentially prepared on the substrate (1) of perovskite solar battery, light absorbing layer (3), electronics
Transport layer (4) and metal electrode (5)；Light absorbing layer (9) are prepared on the glass substrate (8), in the two sides of light absorbing layer (9)
Prepare two metal electrodes (10) and (11)；It is characterized in that, the photodetector further includes thermoelectric generation film (6), pressure
The lower surface of the metal electrode (5) of perovskite solar cell is arranged in power generation plate (7), the thermoelectric generation film (6)；The pressure
Power generation plate (7) is arranged in the lower surface of thermoelectric generation film (6), the perovskite solar battery, thermoelectric generation film, pressure electricity-generating
It connects again with perovskite photodetector after plate three is in parallel.
2. the three-in-one compound photodetector from driving of one kind according to claim 1, which is characterized in that it is described too
Positive energy cell substrate (1) uses tin indium oxide ITO or fluorine-doped tin oxide FTO substrate.
3. a kind of three-in-one compound photodetector preparation method from driving, which is characterized in that connected using inkjet printing technology
Connect perovskite solar battery, thermoelectric generation film, pressure electricity-generating plate, perovskite photodetector；The step of this method includes such as
Under:
(1) perovskite solar cell substrate is pre-processed:
Substrate (1) is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, carries out ultrasound in deionized water by (1a)
Cleaning；
The substrate being cleaned by ultrasonic (1) is carried out UV ozone UV-zone processing by (1b), obtains the substrate (1) pre-processed；
(2) hole transmission layer of perovskite solar battery is prepared:
By hole transmission layer precursor solution drop on the substrate (1) pre-processed, spin coating is carried out using sol evenning machine, after spin coating
Substrate (1), which is placed in thermal station, anneals, and obtains the hole transmission layer (2) of perovskite solar battery；
(3) solution coating method is used, the light absorbing layer (3) of perovskite solar battery is prepared；
(4) electron transfer layer of perovskite solar battery is prepared:
Electron transfer layer precursor solution is spin-coated on the light absorbing layer (3) that preparation is completed using sol evenning machine, obtains perovskite too
The electron transfer layer (4) of positive energy battery；
(5) vacuum coater is used, the metal electrode (5) of perovskite solar battery is prepared；
(6) heat-conducting silicone grease is used, the cell metallic electrode (5) and thermoelectric generation film (6) to perovskite solar energy carry out physics company
It connects；
(7) positive electrode of pressure electricity-generating plate (7) is adhered to the lower surface of the huyashi-chuuka (cold chinese-style noodles) layer of thermoelectric generation film (6)；
(8) glass substrate of perovskite photodetector is pre-processed:
The glass substrate (8) of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound clearly
It washes, is dried up using high-purity nitrogen；
(9) solution coating method is used, the light absorbing layer (9) of perovskite photodetector is prepared；
(10) vacuum coater is used, two metal electrodes (10) and (11) of perovskite photodetector are prepared；
(11) perovskite solar battery, thermoelectric generation film, perovskite photodetector are connected:
Using inkjet printing technology, by the substrate (1) of perovskite solar battery respectively with the anode of thermoelectric generation film (6), pressure
A metal electrode (10) connection of the positive electrode, perovskite photodetector of power power generation plate (7), by perovskite solar battery
Metal electrode (5) respectively with the cathode of thermoelectric generation film (6), the negative electrode of pressure electricity-generating plate (7), perovskite photodetector
Another metal electrode (11) connection.
4. the three-in-one compound photodetector preparation method from driving of one kind according to claim 3, which is characterized in that
Hole transmission layer precursor solution described in step (2) refers to, triphenylamine derivative solution, poly- 3,4-ethylene dioxythiophene: gathers
Styrene sulfonate PEDOT:PSS solution, poly- (3- hexyl thiophene) P3HT solution, cuprous sulfocyanide CuSCN solution, nickel oxide
Any one in NiO solution.
5. the three-in-one compound photodetector preparation method from driving of one kind according to claim 3, which is characterized in that
Solution coating method described in step (3), step (9) refers to, using three kinds of one-step method spin coating, two-step method spin coating, blade coating methods
In any one method.
6. the three-in-one compound photodetector preparation method from driving of one kind according to claim 3, which is characterized in that
Light absorbing layer described in step (3), step (9) refers to that structure is ABX3Any one in the perovskite material of type, wherein A
For MA+、FA+、(CsxMA1-x)+、(CsxFA1-x)+、(FAxMA1-x)+、(CsxFAyMA1-x-y)+One of, B Pb2+, X I-With
And (IxBr1-x)-、(ClxI1-x)-、(ClxBr1-x)-、(I1-x-yBrxCly)-One of.
7. the three-in-one compound photodetector preparation method from driving of one kind according to claim 3, which is characterized in that
Electron transfer layer precursor solution described in step (4) refers to, zinc oxide ZnO solution, stannic oxide SnO2Solution, C60Solution,
[6,6] any one in-phenyl C61 methyl butyrate PCBM solution.
8. the three-in-one compound photodetector preparation method from driving of one kind according to claim 3, which is characterized in that
Metal electrode described in step (5), step (10) is using any one in gold Au, silver Ag, with a thickness of 100~300nm.
9. the three-in-one compound photodetector preparation method from driving of one kind according to claim 3, which is characterized in that
The sintering temperature of inkjet printing technology described in step (11) is 80~120 DEG C, and the time is 10~15min.
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